Silver halide photographic material

ABSTRACT

The object of the present invention is to provide a silver halide light-sensitive material capable of forming a ultra high gradation image by processing in a stable developing solution. 
     The present invention is a silver halide photographic material containing at least one of the compounds represented by Formula (I) or (II): ##STR1## wherein X represents an aliphatic group, an aromatic group, or a heterocyclic group and may be substituted; R 1  represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group; R 2  and R 3  each represent an aliphatic group, an aromatic group, or a heterocyclic group and may be the same or different; and further R 1 , R 2  and R 3  may be substituted and combined with each other to form a ring; ##STR2## wherein X represents an aliphatic group, an aromatic group, or a heterocyclic group and may be substituted; Y represents a --O-- group, a --NR 3  -- group, a --S-- group, a --SO-- group, a --SO 2  -- group, or a --CO-- group; R 1 , R 2  and R 3  each represent an aliphatic group, an aromatic group, or a heterocyclic group and may be the same or different; and R 1  and R 3  may be a hydrogen atom; and further, R 1 , R 2  and R 3  may be substituted and combined with each other to form a ring, and in the case where R 1  and R 2  are combined to form a ring, any one of them may be a single bond.

TECHNICAL FIELD

The present invention relates to a silver halide photographic materialproviding a negative image with a remarkably hard gradation, a highsensitive negative image, and a good dot image quality, or a silverhalide photographic material for forming a direct positive photographicimage, specifically to a photographic material containing a novelcompound as a nucleus forming agent for silver halide.

TECHNICAL BACKGROUND

The addition of a hydrazine compound to a silver halide photographicemulsion or a developing solution is known in U.S. Pat. Nos. 3,730,727(the developing solution in which ascorbic acid and hydrazine arecombined), 3,227,552 (hydrazine is used as an auxiliary developing agentfor obtaining a direct positive color image), 3,386,831(β-monophenylhydrazide of aliphatic carboxylic acid is contained as astabilizer for a silver halide light-sensitive material), and 2,419,975,and The Theory of Photographic Process written by Mees, the thirdedition (1966 ), p. 281.

Among them, it is disclosed particularly in U.S. Pat. No. 2,419,975 thata hydrazine compound is added to obtain a negative image with a hardgradation.

It is described in the same patent specification that the addition ofthe hydrazine compound to a silver bromochloride emulsion and adevelopment in a developing solution having as high pH as 12.8 provide avery hard gradation photographic characteristic with gamma (γ) exceeding10. However, the strong base developing solution having pH close to 13is susceptible to an air oxidation and is instable. Accordingly, it cannot endure storing and use for a long time.

An ultra high gradation photographic characteristic with gamma exceeding10 is very useful for the photo-graphic reproduction of a continuousimage with a dot image useful for a printing plate making or thereproduction of a line drawing either in a negative image or a positiveimage. There has so far generally been used for such the purpose, themethod in which a silver bromochloride emulsion having a silver chloridecontent exceeding 50 mole% preferably 75 mole% is used to carry out adevelopment in a hydroquinone developing solution having the effectiveconcentration of a sulfurous acid ion set at a very low level (usually0.1 mole/liter or less). However, because of the low sulfurous acid ionconcentration in the developing solution in this method, the developingsolution is very unstable and can not endure a storing exceeding threedays.

Further, since these methods require to use the silver bromochlorideemulsion having the relatively high silver chloride content, a highsensitivity has not been able to obtain. Accordingly, it has stronglybeen desired to use a high sensitive emulsion and a stable developingsolution to obtain a ultrahard gradation photographic characteristicuseful for the reproduction of a halftone dot image and a line drawing.

In U.S. Pat. Nos. 4,224,401, 4,168,977, 4,243,739, 4,272,614, and4,323,643, the silver halide emulsions providing the very hard gradationnegative photographic characteristics with a stable developing solutionare disclosed. However, it has been known that the acylhydrazinecompounds used therein have several defects.

That is, it is known that these conventional hydrazines generate anitrogen gas during a development processing, and these gases areconcentrated in a film to form bubbles and damage a photographic image.Further, they are eluted in a development processing solution to exertan adverse affect to a photographic material.

It has so far been known as the means for preventing the elution to thedevelopment processing solution to increase the molecular weight of anucleus forming agent to provide it with an anti-diffusion character.However, it has come to be known that the problem on an aging stabilityis involved in a conventional anti-diffusible nucleus forming agent.That is, the aging of a coating solution containing the nucleus formingagent generates a deposit in the coating solution to deteriorate afiltering performance and further changes the photographic performances.

In the case where a lot of these conventional hydrazines is required fora sensitization and a hard gradation and a particularly high sensitivityis required to the performances of a light-sensitive material, thecombined use with the other sensitizing techniques (for example,enhancing a chemical sensitization, increasing a grain size, and addingthe compounds accelerating a sensitization as described in U.S. Pat.Nos. 4,272,606, and 4,241,164) generally causes an aging sensitizationand the increase in a fog during a storage in some cases.

Accordingly, there have been desired the compounds which can reduce thegeneration of bubbles and the elution to a developing solution, have noproblems on an aging stability, and provide a very hard gradationphotographic characteristic with the addition of a very small amount.

Further, it is described in U.S. Pat. Nos. 4,385,108, 4,269,929, and4,243,739 that hydrazines having a substituent easily adsorbing on asilver halide grain can be used to obtain a photographic performancewith a very hard negative gradation. However, those concretely describedin the above exemplified compounds among the hydrazine compounds havingan adsorbing group have the problem that they cause an agingdesensitization during a storage. Accordingly, it was required to selectthe compounds causing no such the problem.

Meanwhile, the direct positive photographic processes are variouslyavailable, and most useful are the process in which the silver halidegrains fogged in advance are exposed under the presence of adesensitizer and then developed, and the process in which the silverhalide emulsion having a light-sensitive nucleus mainly in the inside ofa silver halide grain is exposed and then developed under the presenceof a nucleus forming agent. The present invention relates to the latter.The silver halide emulsion which has the light-sensitive nucleus mainlyin the inside of the silver halide grain and in which a latent image isformed mainly in the inside of the grain is called an inner latent imagetype silver halide emulsion, and it can be distinguished from the silverhalide grains forming the latent image mainly on a grain surface.

There are known the process in which the internal latent image typesilver halide photographic emulsion is subjected to a surfacedevelopment under the presence of a nucleus forming agent to obtain adirect positive image, and the photographic emulsions or light-sensitivematerials used for such the process.

In the above method for obtaining the direct positive image, the nucleusforming agent may be added to a developing solution. A better reversalcharacteristic can be obtained when it is added to the photographicemulsion layer or other suitable layers of a light-sensitive material toadsorb it on a silver halide grain surface.

There are known as the nucleus forming agent used for the above methodfor obtaining the direct positive image, hydrazines described in U.S.Pat. Nos. 2,563,785 and 2,588,982; the hydrazine and hydrazide seriescompounds described in U.S. Pat. No. 3,227,552; the heterocyclicquaternary salt compounds described in U.S. Pat. Nos. 3,615,615,3,719,494, 3,734,738, 4,094,683, and 4,115,122, British Patent1,283,835, and JP-A-52-3426 (the term "JP-A" as used herein means anunexamined published Japanese patent application) and 52-69613; thethiourea combining type acylphenylhydrazine series compounds describedin U.S. Pat. Nos. 4,030,925, 4,031,127, 4,139,387, 4,245,037, 4,255,511,and 4,276,364, and British Patent 4,012,443; the compounds havingheterocyclic thioamide as an adsorbing group, described in U.S. Pat. No.4,080,207; the phenylacylhydrazine compounds having a heterocyclic grouphaving a mercapto group as an adsorbing group, described in BritishPatent 2,011,397B; the sensitizing dyes having a substituent having anucleus forming action in a molecular structure, described in U.S. Pat.No. 3,718,470; and the hydrazine compounds described in JP-A-59-200230,JP-A-50-212828, and JP-A-59-212829, and Research Disclosure No. 23510(November 1953).

However, it has come to be found that there are involved therein thedefects that any of these compounds have an insufficient activity as thenucleus forming agent and those having a high activity have aninsufficient storing performance and that after they are added to anemulsion, the activities thereof are changed before coating and furtherthe addition of a lot thereof deteriorates a membrane quality.

There are proposed for the purpose of solving these defects, theadsorptive type hydrazine derivatives described in JP-A-60-179743,JP-A-61-170733, JP-A-62-65034, JP-A-62-948, and JP-A-61-270744; thehydrazine derivatives having a heteroaromatic ring residue in amolecule, described in JP-A-62-275247; or the hydrazine derivativeshaving a group for a modification, described in JP-A-62-270948 andJP-A-63-29751. However, there used to be involved therein the problemsthat any of them has an insufficient nucleus forming activity for therequirements to lower pH of a development processing solution in orderto increase the stability of the processing solution (that is, toprevent the deterioration of a developing agent), to shorten aprocessing time in a development, or to decrease a dependency on thefluctuation of a developing solution composition (for example, pH andsodium sulfite) and that an adverse influence due to the elution to thedevelopment processing solution can be seen.

Accordingly, a first object of the present invention is to provide asilver halide photographic material capable of providing a very hardgradation photographic characteristic having a gamma exceeding 10 in astable developing solution.

A second object of the present invention is to provide a negative typesilver halide photographic material containing high activity hydrazinescapable of providing a desired very hard gradation photographiccharacteristic even in a low pH developing solution at a small additionamount without exerting an adverse influence to the photographicperformances.

A third object of the present invention is to provide a direct positivetype silver halide photographic material containing high activityhydrazines capable of providing an excellent reversal characteristiceven in the low pH developing solution.

A fourth object of the present invention is to provide a silver halidephotographic material containing hydrazines which can easily besynthesized and have an excellent storing performance and having a goodaging stability.

A fifth object of the present invention is to provide a silver halidephotographic material in which an emulsion has a good aging stabilityand an activity fluctuation in manufacturing the light-sensitivematerial is small.

DISCLOSURE OF THE INVENTION

These objects of the present invention have been achieved by a silverhalide photographic material having at least one silver halidephotographic emulsion layer, wherein the above photographic emulsionlayer or the other at least one hydrophilic colloid layer contains atleast one of the compounds represented by the following Formula (I) orFormula (II): ##STR3## wherein X represents an aliphatic group, anaromatic group, or a heterocyclic group and may be substituted; R₁represents a hydrogen atom, an alkyl group, an aryl group, an alkoxygroup, an aryloxy group, or an amino group; R₂ and R₃ each represents analiphatic group, an aromatic group, or a heterocyclic group and may bethe same or different; and further R₁, R₂ and R₃ may be substituted andcombined with each other to form a ring; ##STR4## wherein X representsan aliphatic group, an aromatic group, or a heterocyclic group and maybe substituted; Y represents a --O-- group, a --NR₃ -- group, a --S--group, a --SO-- group, a --SO₂ -- group, or a --CO-- group; R₁, R₂ andR₃ each represents an aliphatic group, an aromatic group, or aheterocyclic group and may be the same or different; and R₁ and R₃ maybe a hydrogen atom; and further, R₁, R₂ and R₃ may be substituted andcombined with each other to form a ring, and in the case where R₁ and R₂are combined to form a ring, either one of them may be a single bond.

The present invention will be explained below in detail.

First, Formula (I) will be explained in detail.

In Formula (I), the aliphatic group represented by X is a linear,branched or cyclic alkyl group, an alkenyl group or an alkynyl group.The aromatic group represented by X is a monocyclic or dicyclic arylgroup and there can be enumerated, for example, a phenyl group and anaphthyl group.

The heterocyclic group represented by X is a 3- to 10-membered saturatedor unsaturated heterocyclic group containing at least one of N, O or Satom, and these may be a single ring or further form a condensed ringwith other aromatic rings or heterocycles. The heterocyclic group ispreferably a 5- to 6-membered aromatic heterocyclic group, and preferredare those including a pyridyl group, an imidazolyl group, a quinolinylgroup, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, anisoquinolinyl group, a thiazolyl group, and a benzothiazolyl group.

An aromatic group and a nitrogen-containing heterocyclic group arepreferred as X, and the aromatic group is more preferred as X. An arylgroup is particularly preferred.

X may be substituted with a substituent. There can be enumerated as theexample of the substituent, for example, an alkyl group, an aralkylgroup, an alkenyl group, an alkynyl group, an alkoxy group, an arylgroup, a substituted amino group, an aryloxy group, a sulfamoyl group, acarbamoyl group, an alkylthio group, an arylthio group, a sulfonylgroup, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group,a sulfo group, a carboxyl group, an alkyl- and aryloxycarbonyl group, anacyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamidegroup, a sulfonamide group, a nitro group, an alkylthio group, and aarylthio group, and in addition thereto, the group represented by thefollowing Formula (A): ##STR5## wherein Z represents --CO--, --SO₂ --,or --P(═O) (R₆)--(in which R₆ represents an alkoxy group or an aryloxygroup); L represents a single bond, --O--, --S--, or --NR₇ --(in whichR₇ represents a hydrogen atom, an aliphatic group, or an aromaticgroup); and R₄ and R₅ each represents a hydrogen atom, an aliphaticgroup, an aromatic group, or a heterocyclic group and may be the same ordifferent, or may be combined with each other to form a ring.

Further, X can contain one or a plurality of Formula (A).

In Formula (A), the aliphatic group represented by R₄ is a linear,branched or cyclic alkyl group, an alkenyl group, or an alkynyl group.The aromatic group represented by R₄ is a monocyclic or dicyclic arylgroup and there can be enumerated, for example, a phenyl group and anaphthyl group.

The heterocyclic group represented by R₄ is a 3- to 10-memberedsaturated or unsaturated heterocyclic group containing at least one ofan N, O or S atom, and these may be a single ring or may further form acondensed ring with the other aromatic or hetero rings. The heterocyclicgroup is preferably a 5- to 6-membered aromatic heterocyclic group, andpreferred are those including, for example, a pyridyl group, animidazolyl group, a quinolinyl group, a benzimidazolyl group, apyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolylgroup, and a benzothiazolyl group.

R₄ may be substituted with a substituent. For example, the followingones can be enumerated as the substituent. These groups may further besubstituted.

They are, for example, an alkyl group, an aralkyl group, an alkenylgroup, an alkynyl group, an alkoxy group, an aryl group, a substitutedamino group, an acylamino group, a sulfonylamino group, a ureido group,a urethane group, an aryloxy group, a sulfamoyl group, a carbamoylgroup, an alkylthio group, an arylthio group, a sulfonyl group, asulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfogroup, a carboxyl group, an alkyl- and aryloxycarbonyl group, an acylgroup, a alkoxycarbonyl group, an acyloxy group, a carbonamide group, asulfonamide group, a nitro group, an alkylthio group, and an arylthiogroup. These groups may be combined with each other to form a ring ifpossible.

The aliphatic group represented by R₅ in Formula (A) is a linear,branched or cyclic alkyl group, an alkenyl group, or an alkynyl group.The aromatic group represented by R₅ is a monocyclic or dicyclic arylgroup, and for example, a phenyl group can be enumerated. R₅ may besubstituted with a substituent. For example, those enumerated as thesubstituent for R₄ in Formula (A) can be enumerated as the substituenttherefor.

Further, R₄ and R₅ may be combined with each other to form a ring ifpossible. A hydrogen atom is more preferred as R₅.

Particularly preferred as Z in Formula (A) are --CO-- and --SO₂ --, andL is preferably a single bond or --NR₇ --.

The aliphatic group represented by R₇ in Formula (A) is a linear,branched or cyclic alkyl group, an alkenyl group, or an alkynyl group.The aromatic group represented by R₇ is a monocyclic or dicyclic arylgroup, and for example, a phenyl group is enumerated. R₇ may besubstituted with a substituent. There can be enumerated as thesubstituent, for example, those enumerated as the substituent for R₄ inFormula (A). A hydrogen atom is more preferred as R₇.

In Formula (I), R₁ represents a hydrogen atom, an alkyl group, an arylgroup, an alkoxy group, an aryloxy group, or an amino group. An alkylgroup and an alkoxy group may be any of linear, branched and cyclicones. R₁ may be substituted, and those enumerated as the substituent forR₄ in Formula (A) can be applied as the example of the preferredsubstituent. R₁ is preferably an amino group and particularly preferredis the substituted amino group. When the R₁ represents the substitutedamino group, the nitrogen atom may form a nitrogen-containingheterocycle may be combined with R₂ and/or R₃ to form a cyclicstructure.

The aliphatic group represented by R₂ and R₃ in Formula (I) is a linear,branched or cyclic alkyl group, an alkenyl group, or an alkynyl group.The aromatic group represented by R₂ and R₃ is a monocyclic or dicyclicaryl group and for example, a phenyl group can be enumerated. A furangroup, a thiophene group, and a pyridine group can be enumerated as theheterocyclic group represented by R₂ and R₃. R₂ and R₃ may besubstituted with a substituent. For example, those enumerated as thesubstituent for R₄ in Formula (A) can be enumerated as the substituenttherefor. R₂ and R₃ may be combined with each other to form a ring ifpossible.

In Formula (I), X and one or a plurality of R₁, R₂ and R₃ may have anadsorption accelerating group to silver halide.

The adsorption accelerating group to silver halide, which can besubstituted on R₁, R₂, R₃, or X can be represented by the followingFormula (C):

    Z'--(L').sub.t --                                          Formula (C)

In Formula (C), Z' is the portion adsorbing on a silver halide surface,and L is a divalent linkage group. t is 0 or 1.

There can be enumerated as the preferred example of the portionadsorbing on the silver halide surface represented by Z', a thioamidegroup, a mercapto group, a group having a disulfide group, or a 5- to6-membered nitrogen-containing heterocyclic group.

The thioamide group represented by Z' is a divalent group represented by--CS--(amino)-- and may be a part of a ring structure or an acyclicthioamide group. The useful thioamide group can be selected from thosedisclosed in, for example, U.S. Pat. Nos. 4,030,925, 4,031,127,4,080,207, 4,245,037, 4,255,511, 4,266,013, and 4,276,364, and ResearchDisclosure vol. 151, No. 15162 (November 1976 ) and vol. 176, No. 17626(December 1978).

There can be enumerated as the concrete example of the acyclic thioamidegroup, for example, a thioureido group, a thiourethane group, and adithiocarbamic acid ester group, and as the concrete example of a cyclicthioamide group, for example, 4-thiazolin-2-thione,4-imidazolin-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid,tetrazolin-5-thione, 1,2,4-triazolin-3-thione,1,3,4-thiadiazolin-2-thione, 1,3,4-oxadiazolin-2-thione,benzimidazolin-2-thione, benzoxazolin-2-thione, andbenzothiazolin-2-thione. These may further be substituted.

There can be enumerated as the mercapto group represented by Z', analiphatic mercapto group, an aromatic mercapto group, and a heterocyclicmercapto group (in the case where a nitrogen atom is present next to thecarbon atom to which a --SH group is bonded, the same as a cyclicthioamide group having the relationship of a tautomer therewith and theconcrete examples of this group are the same as those enumerated above).

There can be enumerated as the 5- to 6-membered nitrogen-containingheterocyclic group represented by Z', a 5- to 6-memberednitrogen-containing heterocyclic group consisting of the combination ofnitrogen, oxygen, sulfur, and carbon. Of them, there can be enumeratedas the preferred one, a benzotriazole, a triazole, a tetrazole, anindazole, a benzimidazole, an imidazole, a benzothiazole, a thiazole, abenzoxazole, an oxazole, a thidiazole, an oxadiazle, and a triazine.

These may further be substituted with a suitable substituent. Thesubstituents described as the substituents for X can be enumerated asthe substituents therefor.

Of those represented by Z', a preferred one is a cyclic thioamide group(that is, a mercapto-substituted nitrogen- containing heterocycle, forexample, a 2-mercaptothiadiazole group, 3-mercapto-1, 2,4-triazolegroup, a 5-mercaptotetrazole group, a 2-mercapto-1,3,4-oxadiazole group,and 2-mercaptobenzoxazole group), or a nitrogen-containing heterocyclicgroup (for example, a benzotriazole group, a benzimidazole group, and anindazole group).

The divalent linkage group represented by L' is an atom or atomic groupcontaining at least one of C, N, S, and O. To be concrete, it is singly,for example, an alkylene group, an alkenylene group, an alkynylenegroup, an arylene group, --O--, --S--, --NH--,--N═, --CO--, or --SO₂ --,or the combination thereof.

There can be enumerated as the concrete example, for example, ##STR6##

These may further be substituted with a suitable substituent. Thosedescribed as the substituents for X can be enumerated as thesubstituents therefor. Two or more adsorption accelerating groups tosilver halide represented by Formula (C) may be substituted on any oneof X, R₁, R₂, and R₃ and may be the same or different.

In the case where the compound of the present invention has theadsorption accelerating group to silver halide represented by aboveFormula (C), it is preferred as well since there is not involved theproblem that it brings about an aging desensitization.

Further, X or R₁ to R₃ may contain therein a ballast groupconventionally used in the immobile photographic additives such as acoupler.

The ballast group is an organic group providing a molecular weightsufficient to make it impossible to allow the compound represented byFormula (I) to substantially be diffused to the other layers or aprocessing solution and consists of the combination of one or more of analkyl group, an aryl group, a heterocyclic group, an ether group, athioether group, an amide group, a ureido group, a urethane group, and asulfonamide group. More preferred as the ballast group is a ballastgroup having a substituted benzene ring, and the ballast group havingthe benzene ring substituted with a branched alkyl group is particularlypreferred.

In the case where the compound of the present invention has the aboveballast group, it is preferred as well since it provides an excellentaging stability to an emulsion and there is not involved the problemthat it generates a deposit in a coating solution to deteriorate afiltering performance.

The concrete examples of the compound represented by Formula (I) will beshown below but the present invention will not be limited to thefollowing compounds. ##STR7##

Next, Formula (II) will be explained in detail.

The compound of the present invention represented by Formula (II) ispresent in the form of the compound of the following Formula (II') orexpressed thereby in some occasions. The presence in the form either ofFormula (II) or Formula (II') remains similarly useful for the presentinvention. In the following description, the form of Formula (II) willbe represented and described but the same will be applied even in theform of Formula (II'). ##STR8##

In Formula (II'), all of X, Y, R₁, and R₂ are synonymous with Formula(II).

In Formula (II), the aliphatic group represented by X is a linear,branched or cyclic alkyl group, an alkenyl group or an alkynyl group.The aromatic group represented by X is a monocyclic or dicyclic arylgroup and there can be enumerated, for example, a phenyl group and anaphthyl group.

The heterocyclic group represented by X is a 3- to 10-membered saturatedor unsaturated heterocyclic group containing at least one of an N, O orS atom, and these may be a single ring or further form a condensed ringwith the other aromatic rings or heterocycles. The heterocyclic group ispreferably a 5- to 6-membered aromatic heterocyclic group, and preferredare those including a pyridyl group, an imidazolyl group, a quinolinylgroup, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, anisoquinolinyl group, a thiazolyl group, and a benzothiazolyl group.

An aromatic group and a nitrogen-containing heterocyclic group arepreferred as X and the aromatic group is more preferred as X. An arylgroup is particularly preferred.

X may be substituted with a substituent. There can be enumerated as theexample of the substituent, for example, an alkyl group, an aralkylgroup, an alkenyl group, an alkynyl group, an alkoxy group, an arylgroup, a substituted amino group, an aryloxy group, a sulfamoyl group, acarbamoyl group, an alkylthio group, an arylthio group, a sulfonylgroup, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group,a sulfo group, a carboxyl group, an alkyl- and aryloxycarbonyl group, anacyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamidegroup, a sulfonamide group, a nitro group, an alkylthio group, and aarylthio group, and in addition thereto, the group represented by thefollowing Formula (B): ##STR9##

In Formula (B), Z represents --CO--, --SO₂ --, or --P(═O)(R₆)--(in whichR₆ represents an alkoxy group or an aryloxy group); L represents asingle bond, --O--, --S--, or --NR₇ -- (in which R₇ represents ahydrogen atom, an aliphatic group, or an aromatic group); and R₄ and R₅each represents a hydrogen atom, an aliphatic group, an aromatic group,or a heterocyclic group and may be the same or different, or may becombined with each other to form a ring.

Further, X can contain one or a plurality of Formula (B).

In Formula (B), the aliphatic group represented by R₄ is a linear,branched or cyclic alkyl group, an alkenyl group, or an alkynyl group.The aromatic group represented by R₄ is a monocyclic or dicyclic arylgroup and there can be enumerated, for example, a phenyl group and anaphthyl group.

The heterocyclic group represented by R₄ is a 3- to 10-memberedsaturated or unsaturated heterocyclic group containing at least one ofan N, O or S atom, and these may be a single ring or may further form acondensed ring with other aromatic or heterocycles. The heterocyclicgroup is preferably a 5- to 6-membered aromatic heterocyclic group, andpreferred are those including, for example, a pyridyl group, animidazolyl group, a quinolinyl group, a benzimidazolyl group, apyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolylgroup, and a benzothiazolyl group.

R₄ may be substituted with a substituent. For example, the followingones can be enumerated as the substituent. These groups may further besubstituted.

They are, for example, an alkyl group, an aralkyl group, an alkenylgroup, an alkynyl group, an alkoxy group, an aryl group, a substitutedamino group, an acylamino group, a sulfonylamino group, a ureido group,a urethane group, an aryloxy group, a sulfamoyl group, a carbamoylgroup, an alkylthio group, an arylthio group, a sulfonyl group, asulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfogroup, a carboxyl group, an alkyl- and aryloxycarbonyl group, an acylgroup, a alkoxycarbonyl group, an acyloxy group, a carbonamide group, asulfonamide group, a nitro group, an alkylthio group, and an arylthiogroup. These groups may be combined with each other to form a ring ifpossible.

The aliphatic group represented by R₅ in Formula (B) is a linear,branched or cyclic alkyl group, alkenyl group, or alkynyl group. Thearomatic group represented by R₅ is a monocyclic or dicyclic aryl group,and for example, a phenyl group can be enumerated. R₅ may be substitutedwith a substituent. For example, those enumerated as the substituent forR₄ in Formula (A) can be enumerated as the substituent therefor.

Further, R₄ and R₅ may be combined with each other to form a ring ifpossible. A hydrogen atom is more preferred as R₅.

Particularly preferred as Z in Formula (B) are --CO-- and --SO₂ --, andL is preferably a single bond or --NR₇ --.

The aliphatic group represented by R₇ in Formula (B) is a linear,branched or cyclic alkyl group, alkenyl group, or alkynyl group. Thearomatic group represented by R₇ is a monocyclic or dicyclic aryl group,and for example, a phenyl group can be enumerated. R₇ may be substitutedwith a substituent. There can be enumerated as the substituent, forexample, those enumerated as the substituent for R₄ in Formula (B). Ahydrogen atom is more preferred as R₇.

Preferred as Y in Formula (II) are a --O-- group, a --SO₂ -- group, anda --CO-- group, and a --SO₂ -- group and a --CO-- group are particularlypreferred.

The aliphatic group represented by R₁, R₂ and R₃ in Formula (II) is alinear, branched or cyclic alkyl group, alkenyl group, or alkynyl group.The aromatic group represented by R₁, R₂ and R₃ is a monocyclic ordicyclic aryl group and for example, a phenyl group can be enumerated. Afuran ring, a thiophene ring, and a pyridine ring can be enumerated asthe heterocyclic group represented by R₂ and R₃. Further, R₁ and R₃ maybe a hydrogen atom. R₁, R₂ and R₃ may be substituted with a substituent.For example, those enumerated as the substituent for R₄ in Formula (B)can be enumerated as the substituent therefor. Further, R₁, R₂ and R₃may be combined with each other to form a ring if possible. In the casewhere R₁ and R₂ is combined to form a ring, either one of R₁ and R₂ maybe a single bond.

In Formula (II), X and either one or a plurality of R₁ and R₂ may havean adsorption accelerating group to silver halide.

The adsorption accelerating group to silver halide, which can besubstituted on R₁, R₂, or X can be represented by the following Formula(C'): ##STR10##

In Formula (C'), all of Z', L', and t are synonymous with those inFormula (C). Accordingly, with respect to the portion adsorbing on asilver halide surface represented by Z', the divalent linkage grouprepresented by L', and t, those in Formula (C) can be applied as well toFormula (C') as the preferred examples and concrete examples thereof.

In the case where the compound of the present invention has theadsorption accelerating group to silver halide represented by aboveFormula (C'), it is preferred as well since there is not involved theproblem that it brings about an aging desensitization.

In Formula (II), X or R₁ and R₂ may contain therein a ballast groupconventionally used in the immobile photographic additives such as acoupler.

The ballast group is an organic group providing a molecular weightsufficient to make it impossible to allow the compound represented byFormula (II) to substantially be diffused to the other layers or aprocessing solution and consists of the combination of one or more of analkyl group, an aryl group, a heterocyclic group, an ether group, athioether group, an amide group, a ureido group, a urethane group, and asulfonamide group. More preferred as the ballast group is a ballastgroup having a substituted benzene ring, and the ballast group havingthe benzene ring substituted with a branched alkyl group is particularlypreferred.

In the case where the compound of the present invention has the aboveballast group, it is preferred as well since it provides an excellentaging stability to an emulsion and there is not involved the problemthat it generates a deposit in a coating solution to deteriorate afiltering performance.

The concrete examples of the compound represented by Formula (II) willbe shown below but the present invention will not be limited to thefollowing compounds. Further, any of them will contain the case in whichit is present in the form of Formula (II'). ##STR11##

The compounds of the present invention were synthesized by reactingcorresponding hydrazine with iminochloride under the presence of a base.

The representative examples will be shown below.

(Synthesis of Compound I-1)

Triethylamine (45 ml) was dropped to the mixture of a p-tolylhydrazinehydrochloric acid salt (15.9 g), a raw material compound A stated below(30.6 g) and tetrahydrofuran (200 ml) at -5° C. to 0° C. over the periodof 30 minutes. Stirring was applied for 3 hours while raising atemperature to a room temperature, and then the solution was poured intowater (1 liter) to obtain a crude crystal by filtering. The crudecrystal thus obtained was recrystallized with a methanol- water mixedsolvent to thereby obtain the compound I-1. Yield: 15 g. The chemicalstructure thereof was confirmed with an IR spectrum and an NMR spectrum.##STR12## (Synthesis of Compound II-1)

Triethylamine (30 ml ) was dropped to the mixture of a p-tolylhydrazinehydrochloric acid salt (15.9 g), saccharin chloride (20.0 g) andtetrahydrofuran (200 ml ) at -5° C. to 0° C. over the period of 30minutes. Stirring was applied for 3 hours while raising a temperature toa room temperature, and then the solution was poured into water (1liter) to obtain a crude crystal by filtering. The crude crystal thusobtained was recrystallized with acetonitrile to thereby obtain thecompound II-1. Yield: 11.5 g. The chemical structure thereof wasconfirmed with an IR spectrum and an NMR spectrum.

The other compounds were synthesized in the similar manners.

In incorporating the compound of the present invention into a silverhalide photographic emulsion layer and a hydrophilic colloid layer,after dissolving the compound of the present invention in water or awater miscible organic solvent (alkali hydroxide and tertiary amine maybe added on demand to make a salt for dissolving), the solution may beadded to a hydrophilic colloid solution (for example, a silver halideemulsion, a gelatin aqueous solution, and others) (wherein acid oralkali may be added to adjust pH according to necessity).

The compound of the present invention may be used singly or incombination of two or more kinds. The addition amount of the compound ofthe present invention is preferably 1×10⁻⁶ to 5×10⁻² mole, morepreferably 1×10⁻⁵ to 1×10⁻² mole per mole of silver halide, and asuitable value can be selected according to the character of a silverhalide emulsion combined therewith.

To be concrete, a protective layer and an intermediate layer can beenumerated as the hydrophilic colloid layer containing the compound ofthe present invention.

The compound of the present invention is added preferably to a silverhalide photographic emulsion layer.

The silver halide composition in the silver halide emulsion layer towhich the compound of the present invention is added is not specificallylimited, and there can be enumerated, for example, silver chloride,silver bromochloride, silver bromochloroiodide, silver bromoiodide, andsilver bromide. Particularly in the case where a high sensitivity isrequired, silver bromoiodide is preferably used.

In the case where the compound of Formula (I) or (II) of the presentinvention is used for a hard gradation light-sensitive material for aplate making, the other various additives used for the light-sensitivematerial and the development processing method are not specificallylimited, and those described in the following corresponding portions canbe preferably applied.

    ______________________________________                                        Item            Corresponding portion                                         ______________________________________                                        1)   Nucleus forming                                                                              Formula (II-m) to (II-p) and                                   accelerator    the compound examples II-1 to                                                 II-22 at p. 9, right upper                                                    column, line 13 to p. 16, left                                                upper column, line 10 of JP-A-                                                2-103536; and the compounds                                                   described in JP-A-1-179939.                               2)   Silver halide  p. 20, right lower column, line                                emulsion and   12 to p. 21, left lower column,                                production process                                                                           line 14 of JP-A-2-97937; p. 7,                                 therefor       right upper column, line 19 to                                                p. 8, left lower column, line                                                 12 of JP-A-2-12236; and the                                                   selenium sensitizing process                                                  described in JP-A-5-11389.                                3)   Spectral       p. 8, left lower column, line                                  sensitizing dye                                                                              13 to right lower column, line                                                4 of JP-A-2-12236; p. 16,                                                     right lower column, line 3 to                                                 p. 17, left lower column, line                                                20 of JP-A-2-103536; and                                                      further the spectral                                                          sensitizing dyes described in                                                 JP-A-1-112235, JP-A-2-124560,                                                 JP-A-3-7928, and JP-A-5-11389.                            4)   Surface active p. 9, right upper column, line                                 agent          7 to right lower column, line 7                                               of JP-A-2-12236; and p. 2, left                                               lower column, line 13 to p. 4,                                                right lower column, line 18 of                                                JP-A-2-18542.                                             5)   Anti-fogging agent                                                                           p. 17, right lower column, line                                               19 to p. 18, right upper                                                      column, line 4, and right lower                                               column, lines 1 to 5 of JP-A-2-                                               103526; and further the thio-                                                 sulfinic acid compounds                                                       described in JP-A-1-237538.                               6)   Polymer latex  p. 18, left lower column, lines                                               12 to 20 of JP-A-2-103536.                                7)   Compound having an                                                                           p. 18, right lower column, line                                acid group     6 to p. 19, left upper column,                                                line 1 of JP-A-2-103536.                                  8)   Matting agent, p. 19, left upper column, line                                 sliding agent and                                                                            15 to right upper column, line                                 plasticizer    15 of JP-A-2-103536.                                      9)   Hardener       p. 18, right upper column,                                                    lines 5 to 17 of JP-A-2-103536.                           10)  Dye            dyes described at p. 17, right                                                lower column, lines 1 to 18 of                                                JP-A-2-103536; and solid dyes                                                 described in JP-A-2-294638 and                                                JP-A-5-11382.                                             11)  Binder         p. 3, right lower column, lines                                               1 to 20 of JP-A-2-18542.                                  12)  Anti-black pepper                                                                            the compounds described in U.S.                                agent          Pat. No. 4,956,257, and JP-A-l-                                               118832.                                                   13)  Redox compound the compounds represented by                                                  Formula (I) (particularly the                                                 compound examples 1 to 50) in                                                 JP-A-2-301743; Formulas (R-1),                                                (R-2) and (R-3) and the                                                       compound examples 1 to 75                                                     described at p. 3 to 20 of JP-                                                A-3-174143; and further the                                                   compounds described in JP-A-4-                                                278939.                                                   14)  Monomethine    the compounds of Formula (II)                                  compound       (particularly the compound                                                    examples II-1 to II-26)                                                       described in JP-A-2-287532.                               15)  Dihydroxybenzenes                                                                            p. 11, left upper column to                                                   p. 12 left lower column of JP-                                                A-3-39948; and the compounds                                                  described in EP 452772A.                                  16)  Developing     p. 19, right upper column, line                                solution and   16 to p. 21, left upper column,                                developing process                                                                           line 8 of JP-A-2-103536.                                  ______________________________________                                    

In the case where the compound of Formula (I) or (II) of the presentinvention is used as a fogging agent for a light-sensitive materialaccording to a diffusion transfer process, the other additives for thelight-sensitive material are not specifically limited, and the followingdescribed portions in, for example, JP-A-4-63343 can be referred.

    ______________________________________                                        1)   Dye image-forming:                                                                           page 16, right upper column,                                   material       line 17 to page 18, right                                                     lower column, line 16.                                    2)   Silver halide: page 18, right lower column,                                   emulsion       line 17 to page 19, left                                                      upper column, line 19.                                    3)   Spectral sensitizing:                                                                        page 19, left lower column,                                    dye            lines 1 to 16.                                            4)   Structure of a light-:                                                                       page 19, left lower column,                                    sensitive element                                                                            line 17 to page 20, right                                                     upper column, line 4.                                     5)   Processing:    page 20, right upper column,                                   composition    line 5 to page 21, left                                                       upper column, line 8.                                     6)   Layer structure and:                                                                         page 21, left upper column,                                    others         line 9 to page 22, right                                                      upper column, line 20, and                                                    page 12, right upper column,                                                  line 18 to page 16, line 16.                              ______________________________________                                    

Meanwhile, in the case where the compound of Formula (I) or (II) of thepresent invention is used for an autopositive color light-sensitivematerial, the various additives for the light-sensitive material are notspecifically limited, and the following described portions in, forexample, JP-A-4-34546 can be referred.

    ______________________________________                                        1)   Internal latent:                                                                             page 4, left upper column, line                                image type emulsion                                                                          8 to page 5, right lower                                                      column, line 9.                                           2)   Color coupler: page 16, left upper column, line                                              1 to left lower column, line                                                  19.                                                       3)   Others:        page 16, right lower column,                                                  line 5 to page 18, left upper                                                 column, line 9.                                           ______________________________________                                    

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will further be explained below with the referenceto the examples.

EXAMPLE 1

A silver nitrate aqueous solution and the aqueous solution of potassiumiodide and potassium bromide were simultaneously added to a gelatinaqueous solution maintained at 50° C. for 60 minutes under the presenceof potassium hexachloroiridate (III) of 4×10⁻⁷ mole per mole of silverand ammonia, and pAg was maintained at 7.8 during that time, whereby thecubic monodispersed emulsion having the average grain size of 0.28 μmand the average silver iodide content of 0.3 mole% was prepared. Thisemulsion was desalted by a flocculation process and then inactivegelatin of 40 g per mole of silver was added. Thereafter, whilemaintaining at 50° C., there were added 5,5'-dichloro-9-ethyl-3,3'-bis-(3-sulfopropyl)oxacarbocyanine as a sensitizing dye, anda KI solution of 10⁻³ mole per mole of silver. The emulsion was aged for15 minutes and then the temperature was lowered. This emulsion wasdissolved once again, and there were added at 40° C., 0.02 mole/silverof methyl-hydroquinoe and the hydrazine derivative of the presentinvention or a comparison shown in Table-A. Further added were5-methylbenzotriazole, 4-hydroxy-1,3,3a,7-tetrazaindene, the followingdevelopment accelerators (a) and (b), 0.4 g/m² of the dispersion ofpolyethyl acrylate, and the mixture of the following compounds (c), (d)and (e) as a gelatin hardener. The solution was coated on a polyethyleneterephthalate support (150 μm) having a waterproofing subbing layer (0.5μm) so that the silver amount became 3.4 g/m². ##STR13##

There was coated thereon as a protective layer, the layer containinggelatin 1.5 g/m², the polymethyl methacrylate particles as a mattingagent (average particle size: 2.5 μm) 0.3 g/m², and the followingsurface active agents. ##STR14## [1] Evaluation of a hard gradationperformance:

These samples were exposed to a tungsten light of 3200° K. through anoptical wedge and then developed in the following developing solution-1at 34° C. for 30 seconds, followed by fixing, washing and drying. Thephotographic performances of the sensitivity and gradation obtained areshown in Table-A.

The use of the nucleus forming agent of the present invention provided ahigh sensitivity and a high hard gradation performance.

    ______________________________________                                        [Developing solution-1]                                                       Hydroquinone            50.0    g                                             N-methyl-p-aminophenol  0.3     g                                             Sodium hydroxide        18.0    g                                             5-Sulfosalicylic acid   55.0    g                                             Potassium sulfite       110.0   g                                             Disodium ethylenediaminetetraacetate                                                                  1.0     g                                             Potassium bromide       10.0    g                                             5-Methylbenzotriazole   0.4     g                                             2-Mercaptobenzimidazole-5-sulfonic acid                                                               0.3     g                                             Sodium 3-(5-mercaptotetrazole)benzene-                                                                0.2     g                                             sulfonate                                                                     N-n-butyl diethanolamine                                                                              15.0    g                                             Sodium toluenesulfonate 8.0     g                                             Water was added to      1       liter                                         pH was adjusted to      11.6                                                  (adding potassium hydroxide)                                                  ______________________________________                                    

[2] Photographic performance evaluation in a fatigued developingsolution:

The above developing solution-1 was charged in the automatic developingmachine for a plate making FG660F type (manufactured by Fuji Photo FilmCo., Ltd.), and a development was carried out under the following threeconditions at 34° C. for 30 seconds, followed by carrying out fixing,washing and drying.

[A] After the temperature of the developing solution charged in theautomatic developing machine reaches 34° C., a development processing isimmediately carried out (the development by a fresh solution).

[B] The development processing is carried out in the developing solutionwhich is left for standing for 4 days as it is charged in the automaticdeveloping machine (the development by an air-fatigued solution).

[C] After the developing solution is charged in the automatic developingmachine, the Fuji Film GRANDEX GA-100 film with the size of 50.8 cm×61.0cm is exposed so that the area of 50% thereof is developed, and it issubjected to the development processing in the solution obtained byprocessing 200 sheets per day repeatedly for 5 days. The developingsolution-1 is replenished by 100 ml per sheet of the processed sheetnumber (the development by a large processing-fatigued solution).

The photographic performances thus obtained are shown in Table-A.

The photographic performances obtained in [B] and [C] desirably have nodifference from the photographic performances in [A] in terms of aprocessing running stability.

As can be found from the results in Table-A, the use of the nucleusforming agent of the present invention provides less fluctuation of aphotographic sensitivity even if the developing solution is fatigued.

                                      TABLE-A                                     __________________________________________________________________________                               Photographic                                                                              Photographic performance                                          characteristic                                                                            fluctuation by fatigued solution               Nucleus forming agent                                                                            by fresh solution                                                                         Air-fatigued                                                                         Large processing-               Sample             Added amount                                                                          Sensitivity                                                                         Gradation                                                                           solution                                                                             fatigued solution               No.     Kind       (mol/mol Ag)                                                                          (S)*  (G)** (ΔS.sub.B-A)***                                                                (ΔS.sub.C-A)****          __________________________________________________________________________     1                                                                              Comp.-1                                                                             Blank      --      0      2.6  --     --                               2                                                                              Comp.-2                                                                             Comp. Compound-A                                                                         2.5 × 10.sup.-4                                                                 +0.45 12.3  +0.23  -0.20                            3                                                                              Invent.-1                                                                           Compound I-2                                                                             "       +0.48 15.4  +0.10  -0.09                            4                                                                              Invent.-2                                                                           Compound I-3                                                                             "       +0.51 12.8  +0.09  -0.07                            5                                                                              Invent.-3                                                                           Compound I-4                                                                             "       +0.44 13.2  +0.12  -0.07                            6                                                                              Invent.-4                                                                           Compound I-5                                                                             "       +0.56 15.7  +0.10  -0.10                            7                                                                              Invent.-5                                                                           Compound I-6                                                                             "       +0.51 14.7  +0.08  -0.07                            8                                                                              Invent.-6                                                                           Compound I-7                                                                             "       +0.70 13.6  +0.09  -0.08                            9                                                                              Invent.-7                                                                           Compound I-8                                                                             5.0 × 10.sup.-5                                                                 +0.63 17.3  + 0.10 -0.09                           11                                                                              Comp.-11                                                                            Blank      --      0      2.6  --     --                              12                                                                              Comp.-12                                                                            Comp. Compound-A                                                                         2.5 × 10.sup.-4                                                                 +0.45 12.3  +0.23  -0.20                           13                                                                              Invent.-11                                                                          Compound II-2                                                                            "       +0.65 13.6  +0.13  -0.07                           14                                                                              Invent.-12                                                                          Compound II-7                                                                            "       +0.59 14.7  +0.12  -0.10                           15                                                                              Invent.-13                                                                          Compound II-8                                                                            "       +0.55 15.4  +0.09  -0.08                           16                                                                              Invent.-14                                                                          Compound II-9                                                                            "       +0.51 15.9  +0.10  -0.07                           17                                                                              Invent.-15                                                                          Compound II-10                                                                           "       +0.46 13.8  +0.11  -0.09                           18                                                                              Invent.-16                                                                          Compound II-11                                                                           "       +0.56 18.7  +0.09  -0.08                           19                                                                              Invent.-17                                                                          Compound II-13                                                                           5.0 × 10.sup.-5                                                                 +0.48 17.4  +0.08  -0.07                           __________________________________________________________________________

    ______________________________________                                        [Comparative compound-A]                                                       ##STR15##                                                                    ______________________________________                                        *Sensitivity: based on the sensitivity (log E)                                              of a blank, which is set as a                                                 standard, the sensitivity is shown                                            by the difference therefrom.                                                  Accordingly, the difference of,                                               for example, -0.1 shows that the                                              sensitivity is lower by 0.1 as                                                compared with the blank in terms                                              of log E, that is, the sensitivity                                            is lower by 10 times.                                           **Gradation (G):                                                                            the gradation is the gradient of a                                            straight line obtained by connect-                                            ing the point of 0.3 and the point                                            of 3.0 in the characteristic curve.                                           A larger value shows a harder                                                 gradation.                                                      ***ΔS.sub.B-A :                                                                       the difference between the                                                    sensitivity (S.sub.B) obtained when the                                       development is carried out in an                                              air-fatigued solution and the                                                 sensitivity (S.sub.A) obtained when the                                       development is carried out in a                                               fresh solution.                                                 ***ΔS.sub.C-A :                                                                       the difference between the                                                    sensitivity (S.sub.C) obtained when the                                       development is carried out in a                                               large processing-fatigued solution                                            and the sensitivity (S.sub.A) obtained                                        when the development is carried                                               out in the fresh solution.                                      ______________________________________                                    

EXAMPLE 2

After a silver nitrate aqueous solution and a sodium chloride aqueoussolution were simultaneously added to a gelatin aqueous solutionmaintained at 50° C. under the presence of (NH₄)₃ RhCl₆ of 5.0×10⁻⁶ moleper mole of silver, and then soluble salts were removed by the methodknown well in the art, gelatin was added, and then2-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizerwithout providing a chemical sensitization. This emulsion was themonodispersed emulsion with a cubic crystal form having the averagegrain size of 0.15 μm.

The hydrazine compound was added to this emulsion as shown in Table-B,and there were added a polyethyl acrylate latex of 30 wt% as a solidmatter based on gelatin, and three kinds of the compounds used inExample 1 (that is, the mixture of the compounds (c), (d) and (e)) as ahardener. The solution was coated on a polyester support so that an Agamount became 3.8 g/m² ; Gelatin was 18 g/m². There was coated thereonas a protective layer, the layer containing gelatin 1.5 g/m², thepolymethyl methacrylate particles (average particle size: 2.5 μm) 0.3g/m² as a matting agent, further the following surface active agents asa coating aid, a stabilizer, and a UV absorbing dye, followed by drying.##STR16##

This sample was subjected to an exposure with the daylight printer P-607manufactured by Dainippon Screen Co., Ltd. through an optical wedge andthen to a development processing at 38° C. for 20 seconds, followed byfixing, washing and drying.

The results of the photographic performances are shown in Table-B.

It can be found from the results of Table-B that a high hard gradationcan be obtained in the samples of the present invention as compared withthe samples of a comparative example.

Further, the photographic performances tested in the fatigued developingsolution similarly to Example 1 resulted in showing the preferred resultthat the samples of the present invention had a small fluctuation asshown in Table-B.

                                      TABLE-B                                     __________________________________________________________________________                               Photographic                                                                              Photographic performance                                          characteristic                                                                            fluctuation by fatigued solution               Nucleus forming agent                                                                            by fresh solution                                                                         Air-fatigued                                                                         Large processing-               Sample             Added amount                                                                          Sensitivity                                                                         Gradation                                                                           solution                                                                             fatigued solution               No.     Kind       (mol/mol Ag)                                                                          (S)*  (G)** (ΔS.sub.B-A)***                                                                (ΔS.sub.C-A)****          __________________________________________________________________________     1                                                                              Comp.-1                                                                             Blank      --      0      4.8  --     --                               2                                                                              Comp.-2                                                                             Comp. Compound-A                                                                         1.5 × 10.sup.-3                                                                 +0.16  9.2  +0.11  -0.09                            3                                                                              Invent.-1                                                                           Compound I-2                                                                             "       +0.17 12.3  +0.07  -0.06                            4                                                                              Invent.-2                                                                           Compound I-3                                                                             "       +0.19 11.3  +0.08  -0.06                            5                                                                              Invent.-3                                                                           Compound I-4                                                                             "       +0.21 13.1  +0.06  -0.07                            6                                                                              Invent.-4                                                                           Compound I-5                                                                             "       +0.20 17.1  +0.05  -0.05                            7                                                                              Invent.-5                                                                           Compound I-7                                                                             "       +0.17 16.3  +0.06  -0.07                            8                                                                              Invent.-6                                                                           Compound I-8                                                                             "       +0.24 14.2  +0.05  -0.05                            9                                                                              Invent.-7                                                                           Compound I-12                                                                            3.0 × 10.sup.-4                                                                 +0.25 12.8  +0.03  -0.05                           11                                                                              Comp.-11                                                                            Blank      --      0      4.8  --     --                              12                                                                              Comp.-12                                                                            Comp. Compound-A                                                                         1.5 × 10.sup.-3                                                                 +0.16  9.2  +0.11  -0.09                           13                                                                              Invent.-11                                                                          Compound II-2                                                                            "       +0.19 13.8  +0.04  -0.05                           14                                                                              Invent.-12                                                                          Compound II-7                                                                            "       +0.22 14.3  +0.06  -0.06                           15                                                                              Invent.-13                                                                          Compound II-8                                                                            "       +0.20 15.2  +0.05  -0.05                           16                                                                              Invent.-14                                                                          Compound II-9                                                                            "       +0.18 13.6  +0.05  -0.04                           17                                                                              Invent.-15                                                                          Compound II-10                                                                           "       +0.22 12.8  +0.06  -0.05                           18                                                                              Invent.-16                                                                          Compound II-11                                                                           "       +0.21 13.9  +0.05  -0.03                           19                                                                              Invent.-17                                                                          Compound II-13                                                                           3.0 × 10.sup.-4                                                                 +0.22 17.1  +0.07  -0.04                           __________________________________________________________________________

POSSIBILITY OF UTILIZING IN INDUSTRY

The use of the compound of the present invention of Formula (I) or (II)for a hard gradation light-sensitive material for a plate makingprovides a negative image having a ultrahard gradation and an excellentdot image quality at a high sensitivity.

The use of the compound of the present invention of Formula (I) or (II)as a fogging agent for a silver halide emulsion for a light-sensitivematerial by a diffusion transfer process provides a silver halidephotographic light-sensitive material in which an emulsion has anexcellent aging stability and an activity fluctuation in manufacturingthe light-sensitive material is small.

Further, the use of the compound of the present invention of Formula (I)or (II) for an autopositive type color light-sensitive material providesa direct positive image having an excellent reversal characteristic evenin a stable developing solution.

I claim:
 1. A silver halide photographic material comprising at leastone silver halide photographic emulsion layer, wherein said photographicemulsion layer or another hydrophilic colloid layer contains at leastone of the compounds represented by Formula (I) or (II): ##STR17##wherein X represents an aliphatic group, an aromatic group, or aheterocyclic group; R₁ represents a hydrogen atom, an alkyl group, anaryl group, an alkoxy group, an aryloxy group, or an amino group; R₂ andR₃ each represent an aliphatic group, an aromatic group, or aheterocyclic group and may be the same or different; and further R₁, R₂,and R₃ may be combined with each other to form a ring; ##STR18## whereinX' represents an aliphatic group, an aromatic group, or a heterocyclicgroup; Y represents a --O-- group, a --NR₃ '-- group, a--S-- group, a--SO-- group, a --SO₂ -- group or a --CO-- group; R₁ ', and R₃ ' eachrepresent a hydrogen atom an aliphatic group, an aromatic group, or aheterocyclic group and may be the same or different; R₂ ' represents analiphatic group, an aromatic group, or a heterocyclic group; and furtherR₁ ', R₂ ', and R₃ may be combined with each other to form a ring, andin the case where R₁ 'and R₂ ' are combined to form a ring, either oneof them may be a single bond.
 2. The silver halide photographic materialof claim 1 wherein X of formula (I) is substituted with a substituentselected from the group consisting of an alkyl group, an aralkyl group,an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, anaryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group,an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxy group,a halogen atom, a cyano group, a sulfo group, a carboxyl group, anaryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, anacyloxy group, a carbonamide group, a sulfonamide group, a nitro group,and a group represented by Formula (A) having the following formula:##STR19## wherein Z represents --CO--, --SO₂ -- or --P(=O)(R₆)--; R₆represents an alkoxy group or an aryloxy group; L represents a singlebond, --O--, --S--, or --NR₇ -- R₇ represents a hydrogen atom, analiphatic group, or an aromatic group; R₄ and R₅ each represent ahydrogen atom, an aliphatic group, an aromatic group, or a heterocyclicgroup and may be the same or different, or R₄ and R₅ may be combinedwith each other to form a ring.
 3. The silver halide photographicmaterial of claim 1, wherein X of formula (I) is unsubstituted.
 4. Thesilver halide photographic material of claim 1 wherein R₁ of formula (I)is substituted by a substituent selected from the group consisting of analkyl group, an aralkyl group, an alkenyl group, an alkynyl group, analkoxy group, an aryl group, an acylamino group, a sulfonylamino group,a ureido group, a urethane group, a sulfamoyl group, a carbamoyl group,a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, acyano group, a sulfo group, a carboxyl group, aryloxycarbonyl group, anacyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamidegroup, a sulfonamide group, a nitro group, an alkylthio group, and anarylthio group.
 5. The silver halide photographic material of claim 1,wherein R₁ of formula (I) is unsubstituted.
 6. The silver halidephotographic material of claim 1 wherein R₂ and R₃ of formula (I) areeach substituted by a substituent selected from the group consisting ofan alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, analkoxy group, an aryl group, an acylamino group, a sulfonylamino group,a ureido group, a urethane group, a sulfamoyl group, a carbamoyl group,a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, acyano group, a sulfo group, a carboxyl group, an aryloxycarbonyl group,an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamidegroup, a sulfonamide group, a nitro group, an alkylthio group, and anarylthio group.
 7. The silver halide photographic material of claim 1,wherein R₂ and R₃ of formula (I) are each unsubstituted.
 8. The silverhalide photographic material of claim 1 wherein X' of formula (II) issubstituted with a substituent selected from the group consisting of analkyl group, an aralkyl group, an alkenyl group, an alkynyl group, analkoxy group, an aryl group, an aryloxy group, a sulfamoyl group, acarbamoyl group, an alkylthio group, an arylthio group, a halogen atom,a cyano group, a sulfo group, a carboxyl group, an aryloxycarbonylgroup, an acyl group, an alkoxycarbonyl group, an acyloxy group, acarbonamide group, a sulfonamide group, a nitro group, and a grouprepresented by Formula (B) having the following formula ##STR20##wherein Z represents --CO--, --SO₂ --, or --P(=O)(R₆)--; R₆ representsan alkoxy group or an aryloxy group; L represents a single bond, --O--,--S--, or --NR₇ --; R₇ represents a hydrogen atom, an aliphatic group,or an aromatic group; and R₄ and R₅ each represent a hydrogen atom, analiphatic group, an aromatic group, or a heterocyclic group and may bethe same or different, or R₄ and R₅ may be combined with each other toform a ring.
 9. The silver halide photographic material of claim 1wherein X' of formula (II) is unsubstituted.
 10. The silver halidephotographic material of claim 1 wherein R₁ ' and R₂ ' of formula (II)are each substituted with a substituent selected from the groupconsisting of an alkyl group, an aralkyl group, an alkenyl group, analkynyl group, an alkoxy group, an aryl group, an acylamino group, asulfonylamino group, a ureido group, a urethane group, an aryloxy group,a sulfamoyl group, a carbamoyl group, a sulfinyl group, a hydroxy group,a halogen atom, a cyano group, a sulfo group, a carboxyl group, anaryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, anacyloxy group, a carbonamide group, a sulfonamide group, a nitro group,an alkylthio group, and an arylthio group.
 11. The silver halidephotographic material of claim 1, wherein R₁ ' and R₂ ' of formula (II)are each unsubstituted.